CN106830349B - Polymer modified material for wrapping microorganisms, preparation method thereof and application thereof in N, N-dimethylformamide treatment - Google Patents
Polymer modified material for wrapping microorganisms, preparation method thereof and application thereof in N, N-dimethylformamide treatment Download PDFInfo
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- CN106830349B CN106830349B CN201611239596.6A CN201611239596A CN106830349B CN 106830349 B CN106830349 B CN 106830349B CN 201611239596 A CN201611239596 A CN 201611239596A CN 106830349 B CN106830349 B CN 106830349B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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Abstract
The invention discloses a polymer modified material wrapping microorganisms, a preparation method thereof and application thereof in N, N-dimethylformamide treatment; adding graphene oxide into amide, and then adding triethylamine; then adding acyl chloride under the vacuum condition, in a nitrogen environment and in an ice water bath; then reacting at room temperature for 20-24 hours to prepare pre-modified graphene oxide; dispersing pre-modified graphene oxide in DMF, adding an acrylic compound and a methacrylate compound, and carrying out polymerization reaction in a nitrogen environment by taking AIBN as an initiator to prepare modified graphene oxide; putting the metal net into the solution of the modified graphene oxide, and performing ultrasonic treatment to prepare a polymer modified material; and putting the microorganism into the polymer modified material to prepare the polymer modified material wrapping the microorganism. The modified copper mesh wrapped bacteria can avoid the loss of the bacteria and enrich the concentration of DMF, so that the DMF can be efficiently degraded.
Description
Technical Field
The invention belongs to the field of composite material preparation, and particularly relates to a polymer modified material for wrapping microorganisms, a preparation method thereof and application thereof in N, N-dimethylformamide treatment.
Background
With the development of society and economy, the problem of environmental pollution is endless, and people are concerned about the problem. N, N-Dimethylformamide (DMF) is used as a common solvent in laboratories and factories, and is greatly influenced on the environment and human life due to improper use and random discharge, so that DMF is increasingly treated. Originally, the adsorption method is a simple and direct method with obvious effect, which attracts people's attention, however, because the post-treatment needs desorption, and at the same time, the method has secondary pollution, high cost and low recycling rate. Therefore, finding an economic and sustainable method becomes a hot spot at home and abroad. Biological methods have the advantages of economy, environmental protection and sustainability, but direct use of bacteria to degrade high-concentration DMF can cause toxic effects on bacteria, so that the simple biological method is practically limited, however, in the practical process, bacteria and DMF can be dispersed in solution, so that the degradation efficiency is low.
Disclosure of Invention
The invention aims to provide a polymer modified material wrapping microorganisms and a preparation method thereof.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a preparation method of a polymer modified material for coating microorganisms comprises the following steps:
(1) adding graphene oxide into dimethylacetamide, and then adding triethylamine; then adding acyl chloride under the vacuum condition, in a nitrogen environment and in an ice water bath; then reacting at room temperature for 20-24 hours to prepare pre-modified graphene oxide;
(2) dispersing pre-modified graphene oxide in DMF, adding an acrylic acid compound and an acrylate compound, and carrying out polymerization reaction in a nitrogen environment in the presence of an initiator to prepare modified graphene oxide;
(3) putting the metal net into the solution of the modified graphene oxide, and performing ultrasonic treatment to prepare a polymer modified material;
(4) and putting the microorganism into the polymer modified material to prepare the polymer modified material wrapping the microorganism.
In the technical scheme, in the step (1), graphite flakes are added into a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid, and the mixture is heated and stirred; then adding hydrogen peroxide under the ice-water bath condition to prepare graphene oxide; preferably, the volume ratio of concentrated sulfuric acid to concentrated phosphoric acid is 9-10: 1; the heating and stirring temperature is 40-50 ℃, and the time is 4-6 hours; the graphene material prepared by the invention has abundant functional groups on the surface, and is modified by subsequent modification, and meanwhile, the graphene oxide has a large specific surface area, so that the adsorption performance of the whole material is improved.
In the technical scheme, in the step (1), the mass ratio of graphene oxide to triethylamine to acyl chloride is 1 (3-4) to (3-4); after the reaction at room temperature, washing the product with acetone, and drying to obtain the pre-modified graphene oxide. The original graphene structure is not changed, a modifying group is added, and the modifying group is provided for the subsequent preparation of modified graphene oxide.
In the technical scheme, in the step (2), the mass ratio of the pre-modified graphene oxide to the acrylic acid compound to the methacrylate compound to the initiator is 2 (1-2) to (3-6) to (0.1-0.2); the temperature of the polymerization reaction is 60-70 ℃, and the time is 7-8 hours; and after the polymerization reaction is finished, dropwise adding the product into diethyl ether, centrifuging, washing, and drying in vacuum to obtain the modified graphene oxide. Some ester-containing groups are added to form van der Waals force with DMF, so that the adsorption efficiency is improved.
In the above technical scheme, in the step (3), the metal mesh is a copper mesh; the shape of the copper mesh is suitable for loading microorganisms such as bacteria, such as a bag shape, and the metal mesh is preferably treated and then added into the modified graphene oxide solution, wherein the metal mesh is placed into water for ultrasonic treatment, then placed into DMF for ultrasonic treatment and dried.
In the technical scheme, in the step (3), the power of ultrasonic treatment is 150-200 w, and the time is 5-6 hours; the method can effectively modify the modified graphene oxide onto the metal mesh by a simple method to form a uniform and stable adsorption layer, and can enrich the concentration of DMF, so that the DMF can be efficiently degraded.
According to the technical scheme of the invention, the prepared polymer modified material wrapping the microorganisms combines an adsorption method and a biological method, and gives full play to respective advantages, thereby overcoming the defects caused by a single biological method and an adsorption method in the prior art. Therefore, the invention further discloses the application of the polymer modified material for coating the microorganism in the treatment of the N, N-dimethylformamide; simultaneously discloses the application of the polymer modified material wrapping the microorganism in the treatment of the polluted water body.
The invention also discloses a preparation method of the polymer modified material, which comprises the following steps:
(1) adding graphene oxide into amide, and then adding triethylamine; then adding acyl chloride under the vacuum condition, in a nitrogen environment and in an ice water bath; then reacting at room temperature for 20-30 hours to prepare pre-modified graphene oxide;
(2) dispersing pre-modified graphene oxide in DMF, adding an acrylic acid compound and an acrylate compound, and carrying out polymerization reaction in a nitrogen environment by taking AIBN as an initiator to prepare modified graphene oxide;
(3) and (3) putting the metal net into the solution of the modified graphene oxide, and performing ultrasonic treatment to prepare the polymer modified material.
The invention has the advantages that:
the preparation method of the polymer modified material for coating the microorganisms, disclosed by the invention, has the advantages of low economic cost, easily obtained raw materials and safe and convenient operation, and the modified copper mesh coated bacteria can not only avoid the loss of bacteria, but also enrich the concentration of DMF (dimethyl formamide), so that the DMF can be efficiently degraded, the advantages of the combination of an adsorption method and a biological method can be effectively exerted, and the defects caused by the single biological method and the adsorption method are avoided.
According to the polymer modified material for coating microorganisms, graphene oxide is prepared firstly, pre-modified graphene oxide is obtained, modified graphene oxide is prepared, and the surface of the graphene oxide is modified on the surface of a metal net, wherein the graphene oxide is provided with abundant functional groups on the surface, so that the surface of the graphene oxide can be modified conveniently.
The polymer modified material for wrapping microorganisms modifies modified graphene oxide onto a copper mesh, and degradable DMF strains are put into the copper mesh, so that bacteria can be concentrated to degrade DMF with higher concentration, and DMF wastewater can be efficiently treated; the DMF is enriched, meanwhile, bacteria can be enriched together to efficiently process the DMF, the circulation effect is good, and the method is economical and environment-friendly.
Drawings
FIG. 1 is a photograph of a copper mesh before and after finishing;
FIG. 2 is a thermogravimetric plot before and after graphene oxide modification;
FIG. 3 is an XPS plot before and after modification of graphene oxide;
fig. 4 is an SEM image of graphene oxide, modified graphene oxide, copper mesh, and polymer-modified material;
FIG. 5 is a graph of the degradation efficiency of free bacteria;
FIG. 6 is a cycle chart of the polymer modifying material encapsulating the microorganism.
Detailed Description
Example one
Pre-treating the copper mesh and preparing a model. The method comprises the following specific steps:
the method comprises the steps of firstly making a copper net into a bag-shaped model, then putting the bag-shaped model into water, carrying out ultrasonic treatment for half a day, then putting the bag-shaped model into DMF (dimethyl formamide) for half a day, carrying out ultrasonic treatment, drying in an oven, and then adhering the bag-shaped model into the bag-shaped model by using a hot melt adhesive gun.
And (3) preparing graphene oxide. The method comprises the following specific steps:
preparing a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid in a ratio of 9:1, slowly adding 1.5 parts of graphite flakes, keeping the temperature below 50 ℃, reacting for 5 hours, slowly pouring the solution into ice water while stirring, and finally slowly adding 30% of hydrogen peroxide until the solution becomes bright yellow. Then washed centrifugally with 5% hydrochloric acid and water.
And (3) modifying graphene oxide. The method comprises the following specific steps:
in a round bottom flask, graphene oxide was dispersed in DMAC and triethylamine was added. The reaction system is carried out under vacuum and under the protection of nitrogen, and then methacryloyl chloride is slowly addedWhere (ice water bath) followed by overnight (24 hours) at room temperature, the product was washed with acetone and dried in a vacuum oven to give pre-modified graphene oxide. Dispersing the pre-modified graphene oxide product in DMF, adding methacrylic acid and butyl methacrylate, taking AIBN as an initiator, reacting at 70 ℃ and N2Protecting, reacting for 8 hours, then dropping the product into ether, centrifugally washing, and drying in vacuum. The mass ratio of the graphene oxide to the triethylamine to the methacryloyl chloride is 1:3: 3; the mass ratio of the pre-modified graphene oxide to the methacrylic acid to the butyl methacrylate to the initiator is 2:1:3: 0.1.
And (5) modifying the copper mesh. The method comprises the following specific steps:
putting the prepared model into a modified graphene oxide solution, and continuously performing ultrasonic drying until the surface of the model is completely covered to prepare a polymer modification material; fig. 1 is a photo before and after modification of a copper mesh, and it can be seen that the modified graphene oxide completely covers the surface of the copper mesh. The power of the ultrasonic treatment was 180w and the time was 5 hours.
FIG. 2 is a thermogravimetric diagram of graphene oxide before and after modification; as can be seen from the figure, the amount of polymer modification on the modified graphene oxide is approximately 10%, and the thermal stability of the modified graphene oxide is approximately at 150 ℃.
FIG. 3 is an XPS plot before and after modification of graphene oxide; XPS shows that the pre-modified graphene oxide is successfully modified.
FIG. 4 is an SEM image of graphene oxide, modified graphene oxide, copper mesh and polymer modified material; it can be known from the figure that the modified graphene oxide is successfully prepared, and the modified graphene oxide is successfully modified on the copper mesh because the pore channels of the copper mesh are completely blocked.
The modified copper mesh encapsulates the bacteria. The method comprises the following specific steps:
the polymer modified material for wrapping the microorganism is prepared by putting bacteria (paracoccus denitrificans) into the polymer modified material.
Testing the adsorption performance of the graphene oxide to DMF before and after modification:
100mg of graphene oxide and the modified graphene oxide are respectively put into 500mg/L of DMF and tested at 30 ℃. The model was placed in DMF at 25mg/L, 50mg/L, 100mg/L to measure the change in DMF concentration inside and outside the model. As a result, the adsorption performance of the modified graphene oxide was found to be more efficient than that of the graphene oxide. Meanwhile, the concentration inside and outside the model is measured, and the concentration of DMF around the model is higher than that of DMF at other positions due to the modified graphene oxide on the model, so that the local concentration is favorably improved, and the efficiency is improved.
Degradation test and cycling test on DMF:
pure bacteria and modified copper mesh wrapped with equal mass of bacteria were placed in 50mL MM1 solutions containing 500mg/L and 1000mg/L DMF, respectively, and tested for degradation and cycling performance.
FIG. 5 shows the efficiency of degradation of free bacteria; FIG. 6 is a cycle chart of the polymer modifying material encapsulating the microorganism. The microbial degradation by using the model is more efficient than the degradation by free bacteria, the improvement is about 15 percent, and the cycle efficiency is considerable.
Example two
The method comprises the steps of firstly making a copper net into a bag-shaped model, then putting the bag-shaped model into water, carrying out ultrasonic treatment for half a day, then putting the bag-shaped model into DMF (dimethyl formamide) for half a day, carrying out ultrasonic treatment, drying in an oven, and then adhering the bag-shaped model into the bag-shaped model by using a hot melt adhesive gun.
Preparing a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid in a ratio of 10:1, slowly adding 2g of graphite flakes, keeping the temperature below 40 ℃, reacting for 6 hours, slowly pouring the solution into ice water while stirring, and finally slowly adding 35% of hydrogen peroxide until the solution becomes bright yellow. And then centrifugally washing with 10% hydrochloric acid and water to obtain the graphene oxide.
In a round bottom flask, graphene oxide was dispersed in DMAC and triethylamine was added. The reaction system is carried out under vacuum and under the protection of nitrogen, acryloyl chloride is slowly added into the reaction system (ice water bath), then the reaction system is kept overnight at room temperature for 30 hours, and a product is washed by acetone and dried in a vacuum drying oven to obtain the pre-modified graphene oxide. Dispersing the pre-modified graphene oxide product in DMF, addingAdding methacrylic acid and ethyl methacrylate, using AIBN as initiator, reacting at 60 deg.C and N2And (4) protecting, reacting for 10 hours, then dropwise adding the product into diethyl ether, centrifuging, washing, and drying in vacuum to obtain the modified graphene oxide. The amount of polymer modification on the modified graphene oxide is approximately 12%, and the thermal stability of the modified graphene oxide is approximately 150 ℃. The mass ratio of the graphene oxide to the triethylamine to the acryloyl chloride is 1:4: 4; the mass ratio of the pre-modified graphene oxide to the methacrylic acid to the ethyl methacrylate to the initiator is 2:2:5: 0.2.
Putting the prepared model into a modified graphene oxide solution, and continuously performing ultrasonic drying until the surface of the model is completely covered to prepare a polymer modification material; the modified graphene oxide is successfully prepared, and the modified graphene oxide is successfully modified on the copper mesh because the pore passages of the copper mesh are completely blocked. The power of the ultrasonic treatment was 160w and the time was 5 hours.
The polymer modified material for wrapping the microorganism is prepared by putting bacteria (paracoccus denitrificans) into the polymer modified material. The microbial degradation by using the model is more efficient than the degradation by free bacteria, the improvement is about 14 percent, and the cycle efficiency is considerable.
Through the analysis, the polymer modified material wrapping the microorganisms disclosed by the invention has the advantages of strong DMF (dimethyl formamide) degradation capability, high degradation efficiency, simple and convenient manufacturing process, economy, environmental friendliness, recyclability and the like, so that the polymer modified material has good application in wastewater treatment.
Claims (7)
1. A polymer modified material for coating microorganisms is characterized in that the preparation method of the polymer modified material for coating microorganisms comprises the following steps:
(1) adding graphene oxide into amide, and then adding triethylamine; then adding acyl chloride under the vacuum condition, in a nitrogen environment and in an ice water bath; then reacting at room temperature for 20-24 hours to prepare pre-modified graphene oxide;
(2) dispersing pre-modified graphene oxide in DMF, adding an acrylic acid compound and a methacrylate compound, and carrying out polymerization reaction in a nitrogen environment in the presence of an initiator to prepare modified graphene oxide;
(3) putting the metal net into the solution of the modified graphene oxide, and performing ultrasonic treatment to prepare a polymer modified material;
(4) putting microorganisms into the polymer modified material to prepare the polymer modified material wrapping the microorganisms;
in the step (1), adding graphite flakes into a mixed solution of concentrated sulfuric acid and concentrated phosphoric acid, and heating and stirring; and then adding hydrogen peroxide under the condition of ice-water bath to prepare the graphene oxide.
2. The polymer modification material for coating microorganisms according to claim 1, wherein in the step (1), the volume ratio of concentrated sulfuric acid to concentrated phosphoric acid is 9-10: 1; the heating and stirring temperature is 40-50 ℃, and the time is 4-5 hours.
3. The polymer modified material for coating microorganisms of claim 1, wherein in the step (1), the mass ratio of graphene oxide, triethylamine and acyl chloride is 1 (3-4) to (3-4); after the reaction at room temperature, washing the product with acetone, and drying to obtain the pre-modified graphene oxide.
4. The polymer modified material for coating microorganisms of claim 1, wherein in the step (2), the mass ratio of the pre-modified graphene oxide to the acrylic acid compound to the methacrylate compound to the initiator is 2 (1-2) to (3-6) to (0.1-0.2); the temperature of the polymerization reaction is 60-70 ℃, and the time is 7-8 hours; after the polymerization reaction is finished, dropwise adding the product into diethyl ether, centrifuging, washing, and drying in vacuum to obtain modified graphene oxide; the initiator is AIBN.
5. The microbe-encapsulating polymer modifying material of claim 1, wherein in step (3), the metal mesh is a copper mesh; and (2) adding the processed metal mesh into the modified graphene oxide solution, wherein the metal mesh is put into water for ultrasonic treatment, then put into DMF for ultrasonic treatment, and then dried.
6. The polymer modified material for coating microorganisms of claim 1, wherein in the step (3), the power of ultrasonic treatment is 150-200 w; the time is 5 to 7 hours.
7. Use of the microbe-encapsulating polymer modifying material of claim 1 in the treatment of N, N-dimethylformamide.
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